US4277588A - Preparation of acetylene copolymers - Google Patents

Preparation of acetylene copolymers Download PDF

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Publication number
US4277588A
US4277588A US06/129,828 US12982880A US4277588A US 4277588 A US4277588 A US 4277588A US 12982880 A US12982880 A US 12982880A US 4277588 A US4277588 A US 4277588A
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Prior art keywords
acetylene
carbonyl
dialkynes
polyalkynes
preparation
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US06/129,828
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English (en)
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Herbert Naarmann
Klaus Penzien
Helmut Doerfel
Albrecht Eckell
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BASF SE
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BASF SE
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Assigned to BASF AKTIENGESELLSCHAFT reassignment BASF AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ECKELL ALBRECHT, DOERFEL HELMUT, NAARMANN HERBERT, PENZIEN KLAUS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F238/00—Copolymers of compounds having one or more carbon-to-carbon triple bonds

Definitions

  • the present invention relates to the preparation of acetylene copolymers by polymerizing mixtures of acetylene and dialkynes or polyalkynes with Ziegler catalysts.
  • the present invention relates to a process for the preparation of acetylene copolymers by catalytic polymerization of acetylene with Ziegler catalysts, wherein mixtures of acetylene and dialkynes or polyalkynes are polymerized.
  • Suitable comonomers to use with acetylene are butadiyne, hexadiyne, octadiyne, diethynylbenzene, 1,3,5-triethynylbenzene, 1,2,4-triethynylbenzene, 1,3,5-tris-trimethylsilyl-ethynyl-2,4,6-trimethylsilylbenzene and 1,3,5-tris-propyn-1-yl-2,4,6-trimethylbenzene.
  • monomer mixtures which contain up to 50 mole % of dialkynes or polyalkynes, preferably from 5 to 20 mole % of dialkynes or polyalkynes, are used.
  • the polymerization is most advantageously carried out with Ziegler catalysts which have been prepared from mixtures of aluminum-trialkyls and titanium tetraoxyalkyls.
  • suitable aluminum-trialkyls are aluminum-triethyl, aluminum-triisobutyl and aluminum-trioctyl, the last-mentioned being preferred.
  • the titanium tetraoxyalkyls used are advantageously those where alkyl is of 1 to 10 carbon atoms; in particular, titanium tetraoxybutyl has proved suitable.
  • the weight ratio of aluminum-trialkyl to titanium tetraoxyalkyl in the mixture is from 0.5:1 to 1:0.5, preferably about 1:1.
  • Metal carbonyls eg. iron carbonyl, nickel carbonyl, manganese carbonyl, cobalt carbonyl or molybdenum carbonyl, may also be added to the Ziegler catalysts.
  • the weight ratio of metal carbonyls to aluminum-trialkyl in the mixture is from 0.5:1 to 1:0.5, preferably 1:1.
  • the catalyst mixture is used in an amount of from 0.1 to 10 parts per 100 parts of the mixture of acetylene and other alkynes.
  • the polymerization temperature is advantageously from -90° to +100° C., preferably from -30° to +30° C.
  • the polymerization is advantageously carried out at from 0.1 to 500 bar, preferably at about 50 bar.
  • the polymerization can for example be carried out in an auxiliary fluid.
  • Suitable materials are fluids which are inert toward the polymerization catalysts and toward the monomers, eg. aliphatic oils, aromatics and cycloaliphatics, but also petroleum ether, naphtha and cyclopentadiene.
  • the auxiliary fluids are employed in a weight ratio of the alkynes of from 1:1 to 1,000:1, preferably a ratio of the order of 10:1.
  • the catalysts may be introduced initially, together with the auxiliary fluid, and/or be added continuously during the polymerization.
  • the process gives copolymers of acetylene with dialkynes or polyalkynes which are virtually insoluble.
  • the novel polymers may be used as colored pigments or, because of their film-forming tendency, as colored coatings on metals, glass or plastics; they are also of interest because of their electrical and magnetic properties.
  • a 500 ml vessel was evacuated and flushed with nitrogen, after which 100 mlof toluene and 20 ml of the above catalyst solution were introduced.
  • the reaction vessel was cooled to -50° C. After this temperature had been reached, mixtures of acetylene with various amounts of dialkynes of polyalkynes were introduced into the fluid. After the polymerization had ended, the fluid was siphoned from the reaction vessel and the mixture from the reaction vessel was suction-filtered. The resulting copolymers were washed and dried.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
US06/129,828 1979-03-29 1980-03-13 Preparation of acetylene copolymers Expired - Lifetime US4277588A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2912572 1979-03-29
DE19792912572 DE2912572A1 (de) 1979-03-29 1979-03-29 Verfahren zur herstellung von copolymerisaten des acetylens

Publications (1)

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US4277588A true US4277588A (en) 1981-07-07

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US06/129,828 Expired - Lifetime US4277588A (en) 1979-03-29 1980-03-13 Preparation of acetylene copolymers

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US (1) US4277588A (de)
EP (1) EP0017133B1 (de)
DE (2) DE2912572A1 (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58145420A (ja) * 1981-11-20 1983-08-30 ザ・ブリテイツシユ・ペトロレアム・コンパニ−・ピ−・エル・シ− コヒ−レントなポリ（アセチレン）フイルムの製法
US4408027A (en) * 1980-08-09 1983-10-04 Bayer Aktiengesellschaft Foils of polyacetylene
US4454178A (en) * 1981-11-05 1984-06-12 Basf Aktiengesellschaft Poly(acetylene) films and their production
US4481312A (en) * 1981-04-02 1984-11-06 Bayer Aktiengesellschaft Sheet structures and fibers containing burr-shaped or fibrous, doped polyacetylene particles and process for the production thereof
US4564492A (en) * 1983-04-08 1986-01-14 The British Petroleum Company, P.L.C. Polyacetylene production
US4579921A (en) * 1983-11-29 1986-04-01 Societe Nationale Elf Aquitaine Process for the manufacture of polyacetylene
US4857490A (en) * 1987-08-31 1989-08-15 Hoechst Celanese Corp. Process of manufacturing boron ceramics from carboralated diacetylene polymers
US4946919A (en) * 1987-08-31 1990-08-07 Hoechst Celanese Corp. Boron ceramics from carboralated diacetylene polymers
US5028354A (en) * 1987-10-05 1991-07-02 Regents Of The University Of California Conductive articles of intractable polymers method for making
US5091488A (en) * 1984-11-30 1992-02-25 Director-General Of Agency Of Industrial Science And Technology Polyethylacetylene derivative and process for preparation thereof
US5216102A (en) * 1988-08-05 1993-06-01 Matsushita Electric Industrial Co., Ltd. Process for producing polyacetylene

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3113331A1 (de) * 1981-04-02 1982-10-28 Bayer Ag, 5090 Leverkusen Kletten- bzw. faserfoermige, dotierte polyacetylenteilchen enthaltende thermoplastische kunststoffe und verfahren zu ihrer herstellung
DE3120441A1 (de) * 1981-05-22 1982-12-09 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von filmfoermigem poly(acetylen)
US4394304A (en) * 1982-01-29 1983-07-19 Massachusetts Institute Of Technology Electrically conducting polymer blends
DE3207857A1 (de) * 1982-03-05 1983-09-15 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von poly(acethylen)filmen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB901326A (en) * 1959-04-01 1962-07-18 American Cyanamid Co Polymers and copolymers of diacetylenes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL208266A (de) * 1955-03-18
US4020265A (en) * 1971-02-24 1977-04-26 General Electric Company Polyacetylene tetrapolymers
US4108942A (en) * 1972-03-22 1978-08-22 General Electric Company Polyphenylene polymers and methods for making the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB901326A (en) * 1959-04-01 1962-07-18 American Cyanamid Co Polymers and copolymers of diacetylenes

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
J. Chem. Soc. Chem. Comm., (1977), p. 578 et seq. *
J. Chem. Soc. Japan, Ind. Chem. Sec. 65, (1962), p. 723 et. seq. *
Journal of Pol. Sci. Part A-1, 10, 2033-2043, (1972). *
Trans. Farad. Soc. 64, (1968), p. 823, et. seq. *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4408027A (en) * 1980-08-09 1983-10-04 Bayer Aktiengesellschaft Foils of polyacetylene
US4481312A (en) * 1981-04-02 1984-11-06 Bayer Aktiengesellschaft Sheet structures and fibers containing burr-shaped or fibrous, doped polyacetylene particles and process for the production thereof
US4454178A (en) * 1981-11-05 1984-06-12 Basf Aktiengesellschaft Poly(acetylene) films and their production
JPH0440371B2 (de) * 1981-11-20 1992-07-02 Buriteitsushu Pitorooriamu Co Plc Za
US4496702A (en) * 1981-11-20 1985-01-29 The British Petroleum Company P.L.C. Polyacetylene production
JPS58145420A (ja) * 1981-11-20 1983-08-30 ザ・ブリテイツシユ・ペトロレアム・コンパニ−・ピ−・エル・シ− コヒ−レントなポリ（アセチレン）フイルムの製法
US4564492A (en) * 1983-04-08 1986-01-14 The British Petroleum Company, P.L.C. Polyacetylene production
US4579921A (en) * 1983-11-29 1986-04-01 Societe Nationale Elf Aquitaine Process for the manufacture of polyacetylene
US5091488A (en) * 1984-11-30 1992-02-25 Director-General Of Agency Of Industrial Science And Technology Polyethylacetylene derivative and process for preparation thereof
US4946919A (en) * 1987-08-31 1990-08-07 Hoechst Celanese Corp. Boron ceramics from carboralated diacetylene polymers
US4857490A (en) * 1987-08-31 1989-08-15 Hoechst Celanese Corp. Process of manufacturing boron ceramics from carboralated diacetylene polymers
US5028354A (en) * 1987-10-05 1991-07-02 Regents Of The University Of California Conductive articles of intractable polymers method for making
US5216102A (en) * 1988-08-05 1993-06-01 Matsushita Electric Industrial Co., Ltd. Process for producing polyacetylene

Also Published As

Publication number Publication date
DE2912572A1 (de) 1980-10-09
EP0017133A1 (de) 1980-10-15
DE3061394D1 (en) 1983-01-27
EP0017133B1 (de) 1982-12-22

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